Treatment of hydrocarbons



H. R. JOHNSON TREATMENT OF HYDROCARBONS Aug. s, 1944.

Filed Oct. 17, 1941 w KN *Patented ugQS, 1944 l Unirse stars-s orgies 2,355,077 TREATMENT or maooAnBoNs Harley R. Johnson, Tulsa, Okla.

applicati@ october 1v, 1941, serai No. nessi 9 cams. (ci. cs2-324) This invention relates to a process for treatingA crude petroleum oils to reduce the content of foreign material, particularly salt, which'may be contained therein More specifically, it relates.

to an improved method for desalti'ng and removing othersuspended solid materials which are detrimentaliin subsequent operations if left in the crude petroleum oil'.

The presence of salt, either in the formof an remulsion or. of suspended crystals is objectionable because oi' the fact that when the oil is cracked the salt accelerates the deposition of foreign material including coke in the tubes and other parts of the plant, resulting in increased costs for clean-outs and shorter p'eriods of operation. By removing salt and other foreign material it is possible to improve the results obtained on the'.

One method of `\desalting crude cracking units. oil is by washing with hot water; another method -is to precip tate the material by electrical methpassing the oil in heated condition' through a bed of porous iilterlng material, mixing the` iiltered oil with water, heating it to a temperature below the boiling point of water at the* operating pressure and in the range of about 250 to about 375 F. at a pressure adequate to preventboiling of the system, and separating the desalted oil.

One embodiment of the invention is illustrated i by the accompanying drawing which is diagrammatic and should not be construed as limiting it to the exact conditions given therein.

Crude oil is introduced through line l, containing valve l2,-purnp 3, and valve il. This may be any salt-containing crude oil wherein the salt and other foreign material is present either as yan emulsifled solution of salts, or as salt crystals and/or sediment suspended in the oil. The latter may be surrounded by a more or less diiiicultly permeable illm of oil or asphaltic material which preventsl ready separation from the oil and which also prevents or renders dilcult sufficient rewhich may include sodium chloride and other lsol-- uble salts hereinafter referred to as brine, Yintroducedthrough line '5, containing valve 6, pump as design of the tower is notl limited to any one par` l, and valve 8. The oil is mixed with a neutralizing agent entering through line 9, containing valvellL'pump Il, and valve I2. The neutralizing agent may be alkaline or acidic, depending on whether the oil undergoing treatment is acid or alkaline.

The neutralizing agent mixed with the oil Kand brine may consist of an acid in 4such instances as the crude oil` has an alkaline reaction. These `may include organic ory inorganic acids such as acetic acid, formic acid, proplonic acid and the like', or a mineral acid such as hydrochloric acid,

sulfuric acid, etc. Dilute acid recovered from l sludges from other treating processes in the renery may also be employed.

The mixture passes through line I3, which may contain heat exchanger I4 or /its equivalent, andy valve I5. It is heated to a' temperature of about 200 F., more or less, and a pressure which may be sumcient to force the oil through the filtering materiall described hereinafter. The oil enters the packed tower i6 through a spray maintained near the bottom of the tower.` A liduid level'of brine kept at substantially the neutral point 'by means of the neutralizing agent is maintained in the bottom of the tower below the fil'- tering material, by any known means such as the liquid `level controller I6' which actuatesI valve Il contained in line i8. The oil may also betreated with brine in a separate vessel. The entering mixture of oil and brine passes upward throughthe pool of brine and a separation of the niajor portion of the brine solution takes place.

The Ibrine `solution used may vary considerably in composition but the optimum range of concentration has been found to be about 3-10% by Weight of salts of which sodium chloride may form a major constituent. Azbout 2-15% lby volume of brine is usually used based on the crude,

oil charge. It has been found that the use of brine gives superior results over` those obtained with pure water. Furthermore, this solution may contain small concentrations of a buffer solution, particularly when operating with a slightly alkaline system, for example, between 'l and 8 pH. Brine solution from the `process may be made to the-desired concentration and recycled. Demulsifying or wetting agents such as certain alkali metal phosphates, naphthenates, etc., may be used. Although in vmost cases a pH of about 7 is preferred, the solution 'may be slightly on the alkaline side in some cases.'

The oil passes upwardthrough the tower which contains packing materialdisposed therein. The

are not readily disintegrated by contact with,

water-and/or oil. The exact manner in which the brine treatment followed by the filtering treatment functions is not fully understood. It is known Ythat a smallramount of solid Ysuspended material such as shale or mud, including some salt, is removed but the salt content of the oil is rarely reduced more than about 20-2'5% and the reduction is not of a commercially feasible amount. Microscopic examination of an oil con- A 'taining suspended salt crystals show that they vary in size in the oil as it is produced. The crystals appear to become of a more uniform size after passage through the brine vtreatment and the filter-ing step of the present process. important function of the steps appears to 'be to break up or disintegrate the film of oil or asphaltic material surrounding the suspended salt crystals in such a manner that in the subsequent washing step which is given the oil, the hot water is enabled to contact the salt particles and dissolve them. r I

In any event, the brine treatment and filtration'steps. put the oil in a condition such ,that the final washing and settling steps are more ef- Another fective in removing salt from the oil. Without these two steps, both of which are necessary, the

salt is much more difficult to remove and, in fact, cannot, in many cases, be removed tothe desired extent by ordinary washing methods. It is jrecognized that some oils can be .desalted to a sufficient extent by methods now in use. In many of these cases my process will give improved results. In the main, my invention ,is intended for use with those oils which are not readily desalted by the conventional processes and which therefore present special problems' of salt removal.

The upper portion of tower I6 is usually empty of packing material. It may serve as a means for separating any gas which is dissolved in the crude oil and which is liberated at the temperature and pressure used. The gas passes out of the tower through line I9 and valve 20 which may be actuated by liquid level controller 2| or its .equivalent. This gas may b e sent to a suitable recovery system or may be sent to the crude oil fractionator. containing valve 23, and is mixed with water entering through linev 24 and valve 255 Although a The oil itself is withdrawn through line 22,

mixer is not illustrated it is within the scope of the invention to use one. A

'Ihe water is preferably comparatively soft and may comprise treated boiler water.' 'Ihe mixture of oil and water passes' through line 26, `containing pump 21, valve 28, heat exchanger 29, and valve 30. It is heated to a. temperature of the order of about 250 F. to about 375 F., more or less.

y Lower temperatures give somewhat poorer results a temperature withinthe range of about 275-35'0 'reduced to about 12 to F. is y,usually optimum. The pressure 4 should be adequate to prevent substantial boiling of either the oil or the water. The mixture passes into settler 3l and the desalted oil is removed from line 32,-containing valve 33. The aqueous layer is drawn througlr line 34 and valve 35.

The following examples are given to illustrate the usefulness of the process but should not be interpreted as limiting the process to the exact materials or conditions given thereim.

Example I A West Texas crude oil containing approximately 200 pounds of salt per thousand barrels of oil was treated according to my invention. The oil was mixed with about 5% by volumeV of a l6% brine solution. Sodium hydroxide solution was added to the mixture in sufficient quantity to maintain the brine soluton at about the neutral point and at all times below pH 8, at the end of approximately these conditions of temperature The salt content. of the oil was j 15 pounds per thousand y and pressure.

barrels of oil.

` Example II The West Texas crude oil was treated under similar conditions to those used in Example I except that the filtering material in the tower was cereal straw. This treatment reduced the salt content to less than 20 pounds per thousand barrels of crude oil. In this case the brine solution used in the first step was prepared from the waterseparated in the final step by allowing fit to evaporate to the preferred concentration;

namely, about 6%.

Example III |I'lie West Texas crude oil was treated in a manner similar to that describeqin Example I, using granular pumice as the filtering agent. The salt content was reduced to less than 20 pounds per thousand barrels ofY oil. l

Example yI V In thisV run the West Texas crude oil was treated inl a manner similar to that described in the foregoing examples except that a rock wool. was used as the filtering agent. The salt content was reduced to approximately 15 to 20 pounds per thousand barrels.

Egample V The' West Texas cruder oil was treated as del scribed in Example I but using granular calcined fire clay asthe packing material. The salt content was' reduced to less lthan 25 pounds per `thousand barrels by this treatment.

Inv order to show that the combined steps are essential and that they must be employed' in the l sequence named, a sample of oil was takenimmediately following the filtering treatment;

ithat is, ythe oil had been treated first with the brine and then passed'V through the packing material. At this point the sait'cortent was remaintained duced by not more than 20-25% of the original value. When usingl onlyI the hot water-treat` lment without the previous brine andv ltration 1 treatment the salt content of the oil couldy be reduced to a minimum of about 50-60pounds per i thousand barrels..` If the steps .were.reversed, that is, if the oil were treated lwith hot water and then with the brine and ltered, the desired reduction was not obtained. f- `The oil con' tains about li-60. pounds of salt per thousand' barrels after such a treatment.

When operating according to my invention to piloduce an oil containing less than about 20 pounds of'salt per thousand barrels of oil, it w possible to. operate the cracking plant witl'i t -is type of crude oilA for a matter of ,56days as com- 6. A process for desalting crude hydrocarbon oil which comprises mixing said oil with brine solution maintained yat substantially the/ neutral point, passing said mixture through brine solution maintained at substantially the neutral point and at a temperature of from about 150\ to about 200 F., separating oil from the brine and passing the oil substantially free of brine and at substantially the same temperature through a porous iiltering materialwhich will not disintegrate; under the conditions of treatment,

pared to about 2.5 days operation when treatingthe on withv not water. Even ansi-"5s days of operation the plant was in better condition than after days of operation using crude oil prepared by the other method of salt removal. The

coke deposits were less dense and the mounty of corrosion in the plant was greatly r uceti.

I claim as my invention:

1. A process for desalting' crude petroleum oilA limestone type.

/ 3. The process of. claim 1 wherein the filtering material comprises essentially Icereal straw.

y 4. The process of claiinl wherein the lter-V ing material @comprises essentially a porous mineral which does not disintegrate readily u`nder the treatingmonditions. i f

5.x A process for desalting crude hydrocarbon oil' which comprises treating said ,oil at a temperature of from about to about 200 F.

with brine solution,- co'ntacting the oil with a porous iiltering. material which w'ill'not dis.

` cess of about 200 YF., contacting the oil with a treating the ltered oil with water at a temperatureof from. about 250 to about-B75"` under a` pressure adequate to maintain the mixture in substantially liquid phase, and thereafter 7. AA process for 4desalting. crude hydrocarbon oil which comprises treating said'oil-at atemf.

perature of from'about 150 to about 200 F. with brine solution,.contacting the oil with a`. ltering material comprising caliche of the limestone `type at substantially the .same tenperature. thereafter mixing the Oil with water and heating the mixture to a temperature of from about 250 to about 375 F. undera superatinospheric 'f pressure suiicient to maintain the mixture in lsubsti'intially liquid phase, and separating the ycrude oil from the'water. 1 8. A process for desalting crude hydrocarbon on which comprises mixing said oii with brine solution maintained at substantially the neutral point, passing said mixture throughlbrine solution `maintained at substantially the neutral point and at a temperature of from about 150 to about 200 F., separating oil from the brine and passing the oil substantially'free of..brine and at substantially the same temperature through a filtering material comprising caliche of the limestone type, treating thei'lltered oil with water` at a temperature of from about 250 to about 375 -F. under -a pressure adequate to maintain the mixture iiiA substantially liquidJ phase, and thereafter separating' the desalted 9. A process .fior desaltin`g`,hydrocarbon oil `which comprises treating saidoil with a brine solution at yan elevated temperature not iny exiilteringi bed of porous material which will not integrate under thev conditions vof treatment at substantially, the same temperature, there-v after mixing the oilwith water and heating the -mixtureito a temperature-of from about.;250

to about 375 F. undera superatmospheric pres,

disintegrate under the conditions of treatment, thereafter treating the oil with Water at atemperatire above that used in the brine treatment and ata pressureadeqate to maintain the sure'suiiicient to .maintain the mixture in sub'- stantially liquid phase,` and separating the crude 7 oil'from the water.

AHsystem in substantially liquid phase, and separating the desalted oil'.

. HARLEY'12..,ioerNs'oN.A 

